WO2000032734A1 - Production de granules detergents contenant des agents d'avivage - Google Patents

Production de granules detergents contenant des agents d'avivage Download PDF

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Publication number
WO2000032734A1
WO2000032734A1 PCT/EP1999/009006 EP9909006W WO0032734A1 WO 2000032734 A1 WO2000032734 A1 WO 2000032734A1 EP 9909006 W EP9909006 W EP 9909006W WO 0032734 A1 WO0032734 A1 WO 0032734A1
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Prior art keywords
weight
microns
powder
detergent particles
coarse
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PCT/EP1999/009006
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German (de)
English (en)
Inventor
Bernd Larson
René-Andres ARTIGA GONZÁLEZ
Wilfried Rähse
Herman-Josef Welling
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Henkel Kommanditgesellschaft Auf Aktien
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Publication of WO2000032734A1 publication Critical patent/WO2000032734A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/06—Powder; Flakes; Free-flowing mixtures; Sheets
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D11/00—Special methods for preparing compositions containing mixtures of detergents
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/0039—Coated compositions or coated components in the compositions, (micro)capsules
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/40—Dyes ; Pigments
    • C11D3/42—Brightening agents ; Blueing agents

Definitions

  • the present invention relates to a brightener-containing powder, a process for its preparation and the use of these powder for powdering detergents with a high bulk density.
  • the present invention also relates to a process for producing coarse-grained detergents which contain optical brighteners.
  • Granular detergents usually contain, in addition to the ingredients that are indispensable for the washing process, such as surfactants and builder materials, other components that can be summarized under the term washing aids and that include such different active ingredient groups as foam regulators, graying inhibitors, bleaching agents, bleach activators and color transfer inhibitors.
  • Such auxiliary substances also include substances which are absorbed onto the fibers of washed, clean textiles and which are intended to compensate for the weak yellow coloration of originally white textiles which is usually present after washing. These substances are called optical brighteners. They usually work in the desired sense by converting part of the invisible ultraviolet radiation into longer-wave blue light. The yellowish tone of washed laundry can be attributed to the partial absorption of light in the blue region from the spectrum of white light.
  • optical brightener This partial absorption is compensated for by the increased emission of blue light by the optical brightener, so that the result is the impression of bright white laundry.
  • a side effect of the use of optical brighteners is that the granular detergent containing them also appears bright white, which is positively received by the consumer.
  • Optical brighteners are commercially available either as suspensions or as spray-dried products.
  • the optical brightener is usually added in the form of the commercially available suspension spraying aqueous slurry of the detergent ingredients incorporated. It is known that the achievable bulk density of the granular products produced is limited in this production method. So it is normally not possible to produce detergents with bulk densities above approx. 500 g / 1 by spray drying alone. On the other hand, as compact as possible detergents are required by the consumer.
  • An economically advantageous possibility of introducing optical brighteners via the preparation in the production of compact detergents should now be found, which meets all quality requirements with regard to homogeneity, aspect and flowability of the end product.
  • the disadvantages of the cleaning effort of apparatus, the yellowish or greenish product color and the stickiness or tendency to clump the products should be minimized or completely avoided.
  • the advantages of using non-ionic surfactants to improve the whiteness of the end products should be exploited without having to accept the disadvantages of sticking and clumping.
  • An object of the present invention is therefore a powder for coarse detergents containing
  • the powder has maximum primary particle sizes below 50 microns.
  • Preferred powdering agents have even smaller particle sizes, which makes them even more suitable for homogeneous powdering.
  • Preferred powdering agents have maximum primary particle sizes below 20 ⁇ m, preferably below 10 ⁇ m and in particular below 5 ⁇ m.
  • the powdering agent according to the invention contains 40 to 95% by weight of one or more pure white carrier materials.
  • pure white in the context of the present invention means that the carrier materials used have a so-called whiteness, which according to Berger (see A. Berger, A. Brockes: “Color Measurement in the Textile Industry", BAYER Maschinen Revue, Special Issue 3/1, 1971) with the help of filter color measuring devices, for example the Spectroflash 500 from datacolor international, CH-8305 Dietlihon, of over 60, in particular over 70.
  • this method for whiteness determination on textiles was developed and is suitable but also excellent for whiteness measurement of powders or granular substances, whiteness can also be determined using the Ganz / Griesser method, the basics of color measurement are described in DIN standard 5033.
  • a number of substances are suitable as pure white carriers, it being preferred to use substances which, in addition to their function as powdering agents, perform further functions, for example builder action, in the later detergent.
  • a large number of substances are suitable as a carrier material.
  • inorganic as well as organic substances that are sufficiently white in color. Examples include finely divided substances that are obtained by precipitation.
  • silicates, aluminosilicates, alkali silicates and alkali carbonates or bicarbonates are used as substances.
  • Diatomaceous earth (diatomaceous earth) and finely divided cellulose fibers or derivatives thereof can also be used in the context of the present invention.
  • finely divided zeolites can be used, but also pyrogenic silicas (Aerosil ® ) or silicas obtained by precipitation.
  • Powdering agents preferred in the context of the present invention contain 55 to 85% by weight, preferably 60 to 80% by weight and in particular 65 to 75% by weight of one or more pure white carrier materials, wherein carrier materials from the group of the carbonates, the sulfates, the phosphates, the citrates, the silicates, in particular silicas, and the aluminum silicates, in particular zeolites A, P, X and Y, are preferred.
  • carrier materials from the group of the carbonates, the sulfates, the phosphates, the citrates, the silicates, in particular silicas, and the aluminum silicates, in particular zeolites A, P, X and Y are preferred.
  • the carrier material contained in the powdering agents according to the invention preferably has an oil absorption capacity of at least 20 g / 100 g. However, even more preferably, oil absorption components are used which have a higher oil absorption capacity. Powdering agents are preferred in which the carrier material contained therein has an oil absorption capacity of at least 50g / 100g, preferably at least 80g / 100g, particularly preferably at least 120g / 100g and in particular at least 140g / 100g.
  • the oil absorption capacity is a physical property of a substance that can be determined using standardized methods.
  • the British standard methods BS1795 and BS3483: Part B7.1982 exist, both of which refer to Noim ISO 787/5.
  • a balanced sample of the substance in question is placed on a plate and refined flaxseed oil (density: 0.93) "3" is added dropwise from a burette.
  • the powder is mixed intensively with the oil using a spatula, the addition of oil is continued until a paste of smooth consistency is obtained. This paste should flow or flow without crumbling.
  • the oil absorption capacity is now the amount of the added dropwise. ten oil, based on 100g absorbent and is given in ml / 100g or g / lOOg, whereby conversions about the density of linseed oil are possible without any problems.
  • the powdering agents according to the invention contain one or more optical brighteners.
  • These fabrics which are also called “whiteners", are used in modern laundry detergents because even freshly washed and bleached white laundry has a slight yellow tinge.
  • Optical brighteners are organic dyes that convert part of the invisible UV radiation from sunlight into longer-wave blue light. The emission of this blue light complements the "gap" in the light reflected by the textile, so that a textile treated with an optical brightener appears whiter and brighter to the eye. Since the action mechanism of brighteners presupposes that they are drawn onto the fibers, a distinction is made depending on the "dyed" fibers, for example brighteners for cotton, polyamide or polyester fibers.
  • the commercially available brighteners suitable for incorporation in detergents essentially comprise five structural groups: the stilbene, the diphenylstilbene, the coumarin-quinoline, the diphenylpyrazoline group and the group of the combination of benzoxazole or benzimidazole with conjugated systems.
  • An overview of common brighteners can be found, for example, in G. Jakobi, A. Lschreib “Detergents and Textile Washing", VCH-Verlag, Weinheim, 1987, pages 94 to 100. Suitable are e.g.
  • brighteners of the substituted diphenylstyryl type may be present, e.g.
  • Powdering agents preferred in the context of the present invention contain 7.5 to 50% by weight, preferably 10 to 40% by weight and in particular 15 to 30% by weight, of one or more optical brighteners, brighteners of the dimorpholine type and of distilbene -Type or mixtures of these are preferred.
  • the powdering agents according to the invention can optionally contain up to 10% by weight of further active ingredients and auxiliaries.
  • a content of such substances comes about, for example, from the fact that certain commercial brightener preparations contain substances which are neither attributable to the carriers nor to the brighteners.
  • Such active substances or auxiliaries originate, for example, from the groups of polymers, surfactants, non-aqueous solvents, etc.
  • the powdering agents according to the invention preferably contain less than 7.5% by weight, preferably even less than 5% by weight, of further auxiliaries - or active ingredients, particularly preferred powdering agents being free of such substances.
  • Another object of the present invention is a process for the preparation of powdering agents for coarse detergents, in which a mixture of
  • Comminution machines with very different embodiments come into consideration as mills for the method according to the invention. It is common to all mills that they effect the comminution by means of impact, impact, pressure, friction, shear, etc. of grinding elements which perform rotating, oscillating, tumbling or reciprocating movements.
  • the ball mill is preferably used, in which steel, porcelain or flint balls are rolled in a rotating grinding drum, which shatter the ground material as it rolls along or falls down.
  • a sieve ball mill the falling, ground particles are still removed by a drum sieving sieve.
  • Variants of this type of mill are the vibrating ball mills and the circulation mills, the latter being a combination of ball mill and air classifier.
  • So-called cutting mills are also suitable for carrying out the method according to the invention. They consist of a horizontally or vertically arranged rotor, which is equipped with knives that work against knives anchored in the housing of the mill.
  • fine impact mills can also be used, which include pin mills, mills with a peripheral grinding path and jet mills, for example the cross-flow mill and the spiral jet mill.
  • roller, tube, disc, toothed disc, vibration, bell, spring force, centrifugal, cross, and other mills can also be used for the method according to the invention.
  • the mixture is ground in a ball mill, an annular gap ball mill, a mortar mill or a pin disc mill to maximum primary particle sizes below 20 ⁇ m, preferably below 10 ⁇ m and in particular below 5 ⁇ m.
  • the process according to the invention it is preferred that 55 to 85% by weight, preferably 60 to 80% by weight and in particular 65 to 75% by weight, of one or more pure white support materials, preferably support materials from the group of the carbonates, of Sulfates, the silicates, in particular silicas, and the aluminum silicates, in particular zeolites A, P, X and Y, and 7.5 to 50% by weight, preferably 10 to 40% by weight and in particular 15 to 30% by weight one or more optical brighteners, preferably brighteners of the dimorpholine type and of the distilbene type or mixtures thereof, and up to 10% by weight, preferably up to 7.5% by weight and in particular up to 5% by weight .-% of other auxiliaries or active ingredients are mixed and ground.
  • the powdering agents according to the invention are outstandingly suitable for powdering large-scale detergent particles, so that the present invention further relates to
  • the coarse-particle detergent particles have average particle diameters above 700 ⁇ m, preferably above 800 ⁇ m and in particular above 1000 ⁇ m, and the powder medium has a maximum primary particle size below 20 ⁇ m, preferably below 10 ⁇ m and in particular below 5 ⁇ m.
  • the nonionic surfactants used are preferably alkoxylated, advantageously ethoxylated, in particular primary alcohols having preferably 8 to 18 carbon atoms and an average of 1 to 12 moles of ethylene oxide (EO) per mole of alcohol, in which the alcohol radical has a linear or preferably 2-methyl branching may be or may contain linear and methyl-branched radicals in the mixture, as are usually present in oxo alcohol radicals.
  • EO ethylene oxide
  • alcohol ethoxylates with linear residues of alcohols of native origin with 12 to 18 carbon atoms, for example from coconut, palm, tallow fat or oleyl alcohol, and an average of 2 to 8 EO per mole of alcohol are particularly preferred.
  • Preferred ethoxylated alcohols include, for example, C 12 _ 14 - alcohols with 3 EO or 4 EO, C. 9 ⁇ alcohol with 7 EO, C 13 . 15 alcohols with 3 EO, 5 EO, 7 EO or 8 EO, C I2. , 8 alcohols with 3 EO, 5 EO or 7 EO and mixtures thereof, such as mixtures of C 12.14 alcohol with 3 EO and C 12 8 alcohol with 5 EO.
  • the degrees of ethoxylation given represent statistical averages, which can be an integer or a fraction for a specific product.
  • Preferred alcohol ethoxylates have a narrow homolog distribution (narrow range ethoxylates, NRE).
  • fatty alcohols with more than 12 EO can also be used. Examples of this are tallow fatty alcohol with 14 EO, 25 EO, 30 EO or 40 EO.
  • nonionic surfactants which are used either as the sole nonionic surfactant or in combination with other nonionic surfactants, are alkoxylated, preferably ethoxylated or ethoxylated and propoxylated fatty acid alkyl esters, preferably with 1 to 4 carbon atoms in the alkyl chain, in particular Fatty acid methyl esters, as are described, for example, in Japanese patent application JP 58/217598 or which are preferably prepared by the process described in international patent application WO-A-90713533.
  • alkyl polyglycosides Another class of nonionic surfactants that can be used advantageously are the alkyl polyglycosides (APG).
  • Alkypolyglycosides that can be used satisfy the general formula RO (G) z , in which R denotes a linear or branched, in particular methyl-branched, saturated or unsaturated, aliphatic radical having 8 to 22, preferably 12 to 18, C atoms and G is Is a symbol which stands for a glycose unit with 5 or 6 carbon atoms, preferably for glucose.
  • the degree of glycosidation z is between 1.0 and 4.0, preferably between 1.0 and 2.0 and in particular between 1.1 and 1.4.
  • Linear alkyl polyglucosides ie alkyl polyglycosides, in which the polyglycosyl radical is a glucose radical and the alkyl radical is an n-alkyl radical are preferably used.
  • Nonionic surfactants of the amine oxide type for example N-coconut alkyl-N, N-dimethylamine oxide and N-tallow alkyl-N, N-dihydroxyethylamine oxide, and the fatty acid alkanolamides can also be suitable.
  • the amount of these nonionic surfactants is preferably not more than that of the ethoxylated fatty alcohols, especially not more than half of them.
  • Suitable surfactants are polyhydroxy fatty acid amides of the formula (I),
  • RCO stands for an aliphatic acyl radical with 6 to 22 carbon atoms
  • R for hydrogen, an alkyl or hydroxyalkyl radical with 1 to 4 carbon atoms
  • [Z] for a linear or branched polyhydroxyalkyl radical with 3 to 10 carbon atoms and 3 to 10 hydroxyl groups.
  • the polyhydroxy fatty acid amides are known substances which can usually be obtained by reductive amination of a reducing sugar with ammonia, an alkylamine or an alkanolamine and subsequent acylation with a fatty acid, a fatty acid alkyl ester or a fatty acid chloride.
  • the group of polyhydroxy fatty acid amides also includes compounds of the formula (II)
  • R represents a linear or branched alkyl or alkenyl radical having 7 to 12 carbon atoms
  • R 1 represents a linear, branched or cyclic alkyl radical or an aryl radical having 2 to 8 carbon atoms
  • R 2 represents a linear, branched or cyclic alkyl radical or an aryl radical or an oxyalkyl radical having 1 to 8 carbon atoms
  • C,. 4 -alkyl or phenyl radicals are preferred
  • [Z] stands for a linear polyhydroxyalkyl radical, the alkyl chain of which is substituted by at least two hydroxyl groups. is or alkoxylated, preferably ethoxylated or propoxylated derivatives of this radical.
  • [Z] is preferably obtained by reductive amination of a reduced sugar, for example glucose, fructose, maltose, lactose, galactose, mannose or xylose.
  • a reduced sugar for example glucose, fructose, maltose, lactose, galactose, mannose or xylose.
  • the N-alkoxy- or N-aryloxy-substituted compounds can then, for example according to the teaching of international application WO-A-95/07331, be converted into the desired polyhydroxy fatty acid amides by reaction with fatty acid methyl esters in the presence of an alkoxide as catalyst.
  • Nonionic surfactants preferably contained in the coarse-particle detergent particles come from the group of alkoxylated alcohols. These compounds, also known as fatty alcohol polyglycol ethers or alkyl polyglycol ethers, represent a group of nonionic surfactants which, by alkoxylation, but preferably ethoxylation, of primary fatty alcohols or oxoalcohols in the presence of basic or acidic catalysts at temperatures of 150-200 ° and pressures of 1-10 won in cash.
  • a polyglycol ether mixture of homologs of different degrees of alkoxylation is formed, the distribution of which, depending on the catalyst and the amount of alkoxide, between a Gaussian and the corresponding statistic. of an unselective Schulz-Flory curve can vary. For example, a broad homolog distribution is obtained in the presence of sodium hydroxide and a narrow-range homolog distribution using alkaline earth metal salts.
  • basic catalysts for example sodium methylate in methanol, are preferably used in industry.
  • fatty alcohol ethoxylates are contained in the coarse-particle detergent particles, preference is given to using products with degrees of ethoxylation below 10, for example with average degrees of ethoxylation of 5, 6, 7 or 8.
  • Medium degrees of ethoxylation can also be fractional numbers, although lower degrees such as 1.5 or medium degrees of 5.5 can also be set.
  • the chain length of the fatty alcohols which are converted to the ethoxylates is usually in the range from 8 to 22, preferably from 10 to 20 and in particular from 12 to 18 carbon atoms.
  • a preferred use of the powdering agents according to the invention in the context of the present invention is characterized in that the coarse-particle detergent particles, based on the non-powdered particles, are at least 2.5% by weight, preferably at least 5% by weight and in particular at least 7 5% by weight of nonionic surfactant (s), preferably ethoxylated alcohols.
  • nonionic surfactant preferably ethoxylated alcohols.
  • the coarse-particle detergent particles coated with brightener-containing powder can contain further surface-active substances from the group of anionic, zwitterionic or cationic surfactants, anionic surfactants being clearly preferred for economic reasons and because of their performance spectrum.
  • Anionic surfactants used are, for example, those of the sulfonate and sulfate type.
  • the surfactants of the sulfonate type are preferably C 9 . 13 - Alkylbenzenesulfonates, olefin sulfonates, ie mixtures of alkene and hydroxyalkanesulfonates and disulfonates, as obtained, for example, from C 12 . ⁇ 8 monoolefins with terminal or internal double bond by sulfonation with gaseous sulfur trioxide and subsequent alkaline or acidic hydrolysis of the sulfonation products , into consideration.
  • Alkanesulfonates which are derived from C 12 are also suitable.
  • esters of ⁇ -sulfofatty acids for example the ⁇ -sulfonated methyl esters of hydrogenated coconut, palm kernel or tallow fatty acids, are also suitable.
  • Suitable anionic surfactants are sulfonated fatty acid glycerol esters.
  • Fatty acid glycerol esters are to be understood as meaning the mono-, di- and triesters and their mixtures as obtained in the production by esterification of a monoglycerol with 1 to 3 moles of fatty acid or in the transesterification of triglycerides with 0.3 to 2 moles of glycerol become.
  • Preferred sulfonated fatty acid glycerol esters are the sulfonation products of saturated fat acids with 6 to 22 carbon atoms, for example caproic acid, caprylic acid, capric acid, myristic acid, lauric acid, palmitic acid, stearic acid or behenic acid.
  • alk (en) yl sulfates are the alkali and especially the sodium salts of the sulfuric acid half esters of C 12 -C 18 fatty alcohols, for example from coconut fatty alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol or the C 10 -C 20 oxo alcohols and those half-esters of secondary alcohols of this chain length are preferred. Also preferred are alk (en) yl sulfates of the chain length mentioned which contain a synthetic, straight-chain alkyl radical which is produced on a petrochemical basis and which have a degradation behavior analogous to that of the adequate compounds based on oleochemical raw materials.
  • the C, 2 -C 16 alkyl sulfates and C 12 -C ] 5 alkyl sulfates and C ! 4 -C 15 alkyl sulfates are preferred from the point of view of washing technology.
  • 2,3-alkyl sulfates which are produced for example in accordance with US Patent No. 3,234,258 or 5,075,041 and can be obtained as commercial products from Shell Oil Company under the name DAN ®, are suitable anionic surfactants.
  • Suitable anionic surfactants are also the salts of alkylsulfosuccinic acid, which are also referred to as sulfosuccinates or as sulfosuccinic acid esters and which are monoesters and / or diesters of sulfosuccinic acid with alcohols, preferably fatty alcohols and especially ethoxylated fatty alcohols.
  • Preferred sulfosuccinates contain C 8 . 18 fatty alcohol residues or mixtures thereof.
  • Particularly preferred sulfosuccinates contain a fatty alcohol residue which is derived from ethoxylated fatty alcohols, which in themselves are nonionic surfactants (description see below).
  • alk (en) ylsuccinic acid with preferably 8 to 18 carbon atoms in the alk (en) yl chain or salts thereof.
  • Soaps are particularly suitable as further anionic surfactants.
  • Saturated fatty acid soaps are suitable, such as the salts of lauric acid, myristic acid, palmitic acid, stearic acid, hydrogenated erucic acid and behenic acid, and in particular from natural fatty acids, e.g. Coconut, palm kernel or tallow fatty acids, derived soap mixtures.
  • the anionic surfactants can be in the form of their sodium, potassium or ammonium salts and also as soluble salts of organic bases, such as mono-, di- or triethanolamine.
  • the anionic surfactants are preferably in the form of their sodium or potassium salts, in particular in the form of the sodium salts.
  • builders are the most important ingredients in detergents and cleaning agents.
  • the detergent particles powdered with the powdering agents according to the invention can contain all builders commonly used in washing and cleaning agents, in particular thus zeolites, silicates, carbonates, organic cobuilders and - where there are no ecological prejudices against their use - also the phosphates .
  • the builders described below are also particularly suitable as a carrier material in the powder compositions according to the invention.
  • Suitable crystalline, layered sodium silicates have the general formula NaMSi x O 2x + , ⁇ 2 O, where M is sodium or hydrogen, x is a number from 1.9 to 4 and y is a number from 0 to 20 and preferred values for x 2, 3 or 4.
  • M sodium or hydrogen
  • x is a number from 1.9 to 4
  • y is a number from 0 to 20 and preferred values for x 2, 3 or 4.
  • Such crystalline layered silicates are described, for example, in European patent application EP-A-0 164 514.
  • Preferred crystalline layered silicates of the formula given are those in which M represents sodium and x assumes the values 2 or 3.
  • both ⁇ - and ⁇ -sodium disilicate Na ⁇ i ⁇ 'yH 2 O are preferred, wherein ⁇ -sodium disilicate can be obtained, for example, by the method described in international patent application WO-A-91/08171.
  • Amorphous sodium silicates with a modulus Na, O: SiO 2 from 1: 2 to 1: 3.3, preferably from 1: 2 to 1: 2.8 and in particular from 1: 2 to 1: 2.6, can also be used are delayed in dissolving and have secondary washing properties.
  • the delay in dissolution compared to conventional amorphous sodium silicates can be caused in various ways, for example by surface treatment, compounding, compacting / compression or by overdrying.
  • amorphous is also understood to mean “X-ray amorphous”. This means that the silicates in X-ray diffraction experiments do not provide sharp X-ray reflections, as are typical for crystalline substances, but at most one or more maxima of the scattered X-rays, which have a width of several degree units of the diffraction angle. However, it can very well lead to particularly good builder properties if the silicate particles deliver washed-out or even sharp diffraction maxima in electron diffraction experiments. This is to be interpreted as meaning that the products have microcrystalline areas of size 10 to a few hundred nm, values up to max. 50 nm and in particular up to max. 20 nm are preferred.
  • Such so-called X-ray amorphous silicates which also have a delay in dissolution compared to conventional water glasses, are described, for example, in German patent application DE-A-44 00 024. Compacted compacted amorphous silicates, compounded amorphous silicates and over-dried X-ray amorphous silicates are particularly preferred.
  • the finely crystalline, synthetic and bound water-containing zeolite used is preferably zeolite A and or P.
  • zeolite P zeolite MAP® (commercial product from Crosfield) is particularly preferred.
  • zeolite X and mixtures of A, X and / or P are also suitable.
  • Commercially available and can preferably be used in the context of the present invention for example a co-crystallizate of zeolite X and zeolite A (about 80% by weight of zeolite X) ), which is sold by CONDEA Augusta SpA under the brand name VEGOBOND AX ® and by the formula
  • Suitable zeolites preferably have an average particle size of less than 10 ⁇ m (volume distribution; measurement method: Coulter Counter) and preferably contain 18 to 22% by weight, in particular 20 to 22% by weight, of bound water.
  • phosphates as builder substances, provided that such use should not be avoided for ecological reasons.
  • the sodium salts of orthophosphates, pyrophosphates and in particular tripolyphosphates are particularly suitable.
  • Usable organic builders are, for example, the polycarboxylic acids which can be used in the form of their sodium salts, such as citric acid, adipic acid, succinic acid, glutaric acid, tartaric acid, sugar acids, aminocarboxylic acids, nitrilotriacetic acid (NTA), provided that such use is not objectionable for ecological reasons, and mixtures of these this.
  • Preferred salts are the salts of polycarboxylic acids such as citric acid, adipic acid, succinic acid, glutaric acid, tartaric acid, sugar acids and mixtures of these.
  • the coarse-shaped detergent particles to be powdered can of course contain further ingredients of detergents and cleaning agents, with specific ingredients being described in detail below.
  • Another object of the present invention is a process for the preparation of brightener-hooked detergents, which comprises the steps
  • Process step a) comprises the known production of detergent particles for which there is a wide range of prior art.
  • Step a) of the process according to the invention can thus be carried out in a large number of customary mixing and granulating devices.
  • Suitable mixers and granulators are disclosed, for example, Eirich ® mixer Series R or RV (trademark of Maschinenfabrik Gustav Eirich, Hardheim), the Schugi ® Flexomix, the Fukae ® FS-G mixers (trade marks of Fukae Powtech, Kogyo Co., Japan ), the Lödige ® FM, KM and CB mixers (trademark of Lödige Maschinenbau GmbH, Paderborn) or the Drais ® series T or KT (trademark of Drais- Maschinene GmbH, Mannheim).
  • press agglomeration is another possible method for carrying out process step a).
  • the premix for the coarse-particle detergent particles is compressed and plasticized under pressure and under the action of shear forces, homogenized in the process and then discharged from the apparatus in a shaping manner.
  • the most technically significant press agglomeration processes are extrusion, roller compaction, pelleting and tableting.
  • preferred press agglomeration processes are extrusion, roller compaction and pelletization.
  • the premix for the coarse-particle detergent particles is preferably fed continuously to a planetary roller extruder or a 2-shaft extruder or 2-screw extruder with a co-rotating or counter-rotating screw guide, its housing and its extruder pelletizing head on the predetermined extrusion temperature can be heated.
  • the premix is compressed, plasticized, extruded in the form of fine strands through the perforated die plate in the extruder head and finally the ex under pressure, which is preferably at least 25 bar, but can also be lower at extremely high throughputs depending on the apparatus used - Trudat preferably reduced to approximately spherical to cylindrical granules by means of a rotating knives.
  • the hole diameter of the perforated nozzle plate and the strand cut length are matched to the selected granulate dimension.
  • the production of granules of an essentially uniformly predeterminable particle size succeeds, and in particular the absolute particle sizes can be adapted to the intended use.
  • particle diameters up to at most 8 mm are preferred.
  • Important embodiments provide for the production of uniform granules in the millimeter range, for example in the range from 0.5 to 5 mm and in particular in the range from approximately 0.8 to 3 mm.
  • the length / diameter ratio of the chopped-off primary granules is in the range from about 1: 1 to about 3: 1.
  • small amounts of dry powder for example zeolite powder such as zeolite NaA powder, can also be used in this step.
  • step c ie the powdering with the brightener-containing powder detergent, in the rounding device.
  • This shaping / powdering can be done in standard rounding machines. Care should be taken to ensure that only small amounts of fine grain are produced in this stage.
  • Extrusion as a manufacturing process for detergents and cleaning agents is described in detail, for example, in European Patent EP 486 592 (Henkel KGaA).
  • extrusions / pressings can also be carried out in low-pressure extruders, in the Kahl press (extrusion press from Amandus Kahl, Reinbek near Hamburg) or in the extruder (Hosokawa Bepex).
  • Kahl press extrusion press from Amandus Kahl, Reinbek near Hamburg
  • Hosokawa Bepex it is also preferred in the other production processes to feed the resulting primary granules / compactates to a further shaping processing step, in particular a rounding, so that ultimately spherical to approximately spherical (pearl-shaped) grains can be obtained.
  • step a) of the method according to the invention is carried out by means of roller compaction.
  • the premix for the coarse-particle detergent particles is metered in between two smooth rollers or with recesses of a defined shape and rolled out under pressure between the two rollers to form a sheet-like compact, the so-called Schülpe.
  • the rollers exert a high line pressure on the premix and can be additionally heated or cooled as required.
  • smooth rollers smooth, unstructured sliver belts are obtained, while by using structured rollers, correspondingly structured slugs can be produced in which, for example, certain shapes of the later coarse-particle detergent particles can be specified.
  • the sliver belt is subsequently broken up into smaller pieces by a knock-off and comminution device and can be processed into granules in this way, which can be further tempered by further surface treatment processes, in particular brought into an approximately spherical shape and subsequently powdered (process step c)).
  • step a) of the method according to the invention is carried out by means of pelleting.
  • the premix for the coarse-particle detergent particles is applied to a perforated surface and pressed through the holes by means of a pressure-producing body with plasticization.
  • the premix is compressed under pressure, plasticized, pressed through a perforated surface by means of a rotating roller in the form of fine strands and finally comminuted into granules using a knock-off device.
  • the most varied configurations of the pressure roller and perforated die are conceivable here.
  • step a) of the method according to the invention is described, for example, in German laid-open specification DE 38 16 842 (Schlüter GmbH).
  • the ring die press disclosed in this document consists of a rotating ring die penetrated by press channels and at least one press roller which is operatively connected to its inner surface and which presses the material supplied to the die space through the press channels into a material discharge.
  • the ring die and the press roller can be driven in the same direction, which means that a reduced shear stress and thus a lower temperature increase in the premix can be achieved.
  • the coarse-particle detergent particles produced in process step a) are produced by granulation, agglomeration or press agglomeration, in particular by wet granulation, roller compaction, pelleting or extrusion.
  • the preferred ranges already mentioned for the use according to the invention apply to the particle sizes of particles to be powdered and powdering agent.
  • the coarse-particle detergent particles produced in step a) have average particle diameters above 700 ⁇ m, preferably above 800 ⁇ m and in particular above 1000 ⁇ m
  • the powder agent produced in step b) has a maximum primary particle size below 20 ⁇ m, preferably below 10 ⁇ m and in particular below 5 ⁇ m.
  • the coarse-particle detergent particles produced in step a) preferably contain surfactants, a content of at least at least 2.5% by weight, preferably at least 5% by weight and in particular at least 7.5% by weight, of one or more nonionic surfactants, preferably ethoxylated alcohols, is preferred.
  • step a) it is preferred to produce the detergent particles, which preferably contain surfactants, in step a) in a mixer / granulator.
  • This procedure has the advantage that the powder to be applied can be introduced into the same apparatus. In this way, only one mixer / granulator is required for process steps a) and c).
  • Methods according to the invention are preferred in which steps a) and c) are carried out in a mixer / granulator (in the sense of one and the same).
  • Particularly preferred are processes in which process steps a) and c) are carried out in a slow-running mixer, e.g. a Lödige ploughshare mixer, at speeds of 80 to 300 rpm for the mixing tools.
  • this mixer It is particularly advantageous to divide this mixer into two chambers.
  • the granulation takes place in the larger chamber, while the granules are powdered in the smaller chamber.
  • liquids can be injected into this second mixer in order to enhance the effect of the solid coating with an additional coating.
  • Additional coating materials are preferably polymer or water glass solutions.
  • Another possibility is to operate the Lödige mixer in batches, the finely divided powder containing Auheller being added separately at the end of the granulation.
  • the contents of the mixer can then be discharged into an interim storage facility or onto a conveyor belt, from where the downstream parts of the system (fluidized bed dryer, sieve, etc.) continue to be operated.
  • Process step b) the production of the brightener-containing powder, has already been described in detail as a separate process according to the invention, reference being made to the above statements.
  • process step c) of the process according to the invention the finely divided brightener-containing powder is applied to the coarse-particle detergent particles, it being possible to use the powdering methods familiar to the person skilled in the art.
  • the powdering agents produced in step b) are applied to the laundry detergent particles produced in step a) by mixing in the weight ratio of laundry detergent particles to powdering agent from 400: 1 to 25: 1, preferably from 200: 1 to 50: 1 and in particular from 150: 1 to 75: 1.
  • the detergent particles produced in step a) can contain further detergent ingredients, in particular from the groups of bleaching agents, bleach activators, enzymes, pH regulators, dyes, foam inhibitors, anti-redeposition agents, graying inhibitors, color transfer inhibitors and corrosion inhibitors and mixtures be mixed in from this.
  • the detergent particles produced in step a) contain surfactant (s), in particular nonionic surfactant (s) and, preferably, ethoxylated alcohols, this does not result in the other granular components of the preparation are covered by the powder, but only the detergent particles containing surfactant are powdered off. Due to the interaction of nonionic surfactant and powder agent described above, the initially pale greenish color of the powdered detergent particles in the further product path changes to a bright white color within a few minutes.
  • ingredients described below can also be added to the detergent particles that have already been powdered only after carrying out process step c).
  • bleaching agents are, for example, peroxypyrophosphates, citrate perhydrates and H 2 O 2 -producing peracidic salts or peracids, such as perbenzoates, peroxophthalates, diperazelaic acid, phthaloiminoperic acid or diperdodecanedi- acid.
  • Typical organic bleaching agents are the diacyl peroxides, such as dibenzoyl peroxide.
  • Other typical organic bleaching agents are peroxy acids, examples of which include alkyl peroxy acids and aryl peroxy acids.
  • Preferred representatives are (a) the peroxybenzoic acid and its ring-substituted derivatives, such as alkyl peroxybenzoic acids, but also peroxy- ⁇ -naphthoic acid and magnesium monoperphthalate, (b) the aliphatic or substituted aliphatic peroxyacids, such as peroxylauric acid, peroxystearic acid, ⁇ -phthalimoxyhexanoic acid [hexoxyacid] oxaloacetic acid (PAP)], o-carboxybenzamidoperoxycaproic acid, N-nonenylamidoperadipic acid and N-nonenylamidopersuccinate, and (c) aliphatic and araliphatic peroxydicarboxylic acids, such as 1,12-diperoxycarboxylic acid, 1,9-diperoxyazelaic acid, diperocyseboxyacid, diperoxyacid acid, diperoxyacid acid, diperoxy acid, Decy
  • bleach activators can be incorporated.
  • Bleach activators which can be used are compounds which, under perhydrolysis conditions, give aliphatic peroxocarboxylic acids having preferably 1 to 10 C atoms, in particular 2 to 4 C atoms, and / or optionally substituted perbenzoic acid.
  • Suitable substances are those which carry O- and / or N-acyl groups of the number of carbon atoms mentioned and / or optionally substituted benzoyl groups.
  • TAED tetraacety
  • Suitable enzymes are those from the class of proteases, lipases, amylases, cellulases or mixtures thereof.
  • Bacterial strains or fungi such as Bacillus subtilis, Bacillus licheniformis and Streptomyces griseus are particularly suitable enzymatic agents.
  • Proteases of the subtilisin type and in particular proteases which are obtained from Bacillus lentus are preferably used.
  • Enzyme mixtures for example of protease and amylase or protease and lipase or protease and cellulase or of cellulase and lipase or of protease, amylase and lipase or protease, lipase and cellulase, but in particular mixtures containing cellulase, are of particular interest.
  • Peroxidases or oxidases have also proven to be suitable in some cases.
  • the enzymes can be adsorbed on carriers and / or embedded in coating substances in order to protect them against premature decomposition.
  • components can also be included which have a positive influence on the oil and fat washability from textiles (so-called soil repellents). This effect becomes particularly clear when a textile is soiled that has already been washed several times beforehand with a detergent according to the invention which contains this oil and fat-dissolving component.
  • the preferred oil- and fat-dissolving components include, for example, nonionic cellulose ethers such as methyl cellulose and methyl hydroxypropyl cellulose with a proportion of methoxyl groups of 15 to 30% by weight and of hydroxypropoxyl groups of 1 to 15% by weight, in each case based on the nonionic cellulose ether, and the polymers of phthalic acid and / or terephthalic acid or their derivatives known from the prior art, in particular polymers of ethylene terephthalates and / or polyethylene glycol terephthalates or anionically and / or nonionically modified derivatives thereof. Of these, the sulfonated derivatives of phthalic acid and terephthalic acid polymers are particularly preferred.
  • Colorants and fragrances can be added to the detergent particles in order to improve the aesthetic impression of the products and, in addition to the softness, to provide the consumer with a visually and sensorially "typical and unmistakable" product.
  • Individual fragrance compounds for example the synthetic products of the ester, ether, aldehyde, ketone, alcohol and hydrocarbon type, can be used as perfume oils or fragrances.
  • Fragrance compounds of the ester type are, for example, benzyl acetate, phenoxyethyl isobutyrate, p-tert-butylcyclohexyl acetate, linalyl acetate, dimethylbenzylcarbyl acetate, phenylethyl acetate, linalyl benzoate, benzyl formate, Ethyl methylphenyl glycinate, allyl cyclohexyl propionate, styrallyl propionate and benzyl salicylate.
  • the ethers include, for example, benzyl ethyl ether
  • the aldehydes include, for example, the linear alkanals with 8-18 C atoms, citral, citronellal, citronellyloxyacetaldehyde, cyclamen aldehyde, hydroxycitronellal, lilial and bourgeonal
  • the ketones include, for example, the ionone, c-isomethyl ionone and methyl cedryl ketone
  • the alcohols anethole, citronellol, eugenol, geraniol, linalool, phenylethyl alcohol and terpineol
  • the hydrocarbons mainly include the terpenes such as limonene and pinene.
  • Perfume oils of this type can also contain natural fragrance mixtures such as are obtainable from plant sources, for example pine, citrus, jasmine, patchouli, rose or ylang-ylang oil. Also suitable are muscatel, sage oil, chamomile oil, clove oil, lemon balm oil, mint oil, cinnamon leaf oil, linden blossom oil, juniper berry oil, vetiver oil, olibanum oil, galbanum oil and labdanum oil as well as orange blossom oil, neroliol, orange peel oil and sandalwood oil.
  • the colorant content of detergents and cleaning agents is usually less than 0.01% by weight, while fragrances can make up up to 2% by weight of the entire formulation.
  • the fragrances can be incorporated directly into the detergents, but it can also be advantageous to apply the fragrances to carriers which increase the adhesion of the perfume to the laundry and ensure a long-lasting fragrance for the textiles due to a slower fragrance release.
  • Cyclodextrins for example, have proven useful as such carrier materials, and the cyclodextrin-perfume complexes can additionally be coated with further auxiliaries.
  • dyes In order to improve the aesthetic impression of the agents according to the invention, they can be colored with suitable dyes.
  • Preferred dyes the selection of which is not difficult for the person skilled in the art, have a high storage stability and insensitivity to the other ingredients of the compositions and to light, and no pronounced substantivity to textile fibers, in order not to dye them. Examples:
  • the base granules contain approximately 4% nonionic surfactant (3.5% via extrusion + ethoxylated tallow alcohol from the tower powder). Another 0.4% nonionic surfactant is sprayed onto the surface via a suspension of brightener in nonionic surfactant.
  • the total amount of nonionic surfactant can and should be quite higher, with no product caking according to the above statements.
  • the extrudate contains approximately 7.5% non-ionic surfactants:
  • a tower powder of the following composition was produced by spray drying and served as the basis for a premix to be extruded:
  • This tower powder was mixed with other substances and in a Lihotzky-2 screw extruder at a temperature of 80 ° C to crude extrudates with a medium Extruded particle size of 1.2 mm.
  • the premix / extrudate composition was as follows:
  • the surface of the extrudate particles was evenly coated with brightener powder in this mixing process. It is striking that the other granular components of the preparation were not covered by the powder.
  • the initially pale greenish color of the extrudate particles at the mixer outlet turned into a brilliant white color within a few minutes.
  • the Berger whiteness was above 100.
  • the whitening powder used was previously prepared by grinding the raw materials listed below together in a pin disc mill in a circuit up to a maximum particle size below 5 ⁇ m (primary particles according to SEM image):

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  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
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  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Detergent Compositions (AREA)

Abstract

L'invention concerne des agents pulvérulents pour détergents à grains grossiers, qui confèrent à des particules détergentes à pulvériser, notamment des particules détergentes contenant des tensioactifs, des propriétés optiques remarquables. Ces agents pulvérulents contiennent entre 40 et 95 % en poids d'un ou de plusieurs matériaux supports blancs purs, entre 5 et 80 % en poids d'un ou de plusieurs agents d'avivage, ainsi que jusqu'à 15 % en poids d'autres auxiliaires ou principes actifs et présentent des dimensions maximales de particules primaires inférieures à 50 νm.
PCT/EP1999/009006 1998-12-02 1999-11-23 Production de granules detergents contenant des agents d'avivage WO2000032734A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE1998155677 DE19855677A1 (de) 1998-12-02 1998-12-02 Herstellung Aufheller-haltiger Waschmittel-Granulate
DE19855677.2 1998-12-02

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WO2000032734A1 true WO2000032734A1 (fr) 2000-06-08

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE10062007B4 (de) * 2000-12-13 2010-03-18 Henkel Ag & Co. Kgaa Feste waschaktive Zubereitung mit verbessertem Einspülverhalten
DE10148851A1 (de) * 2001-10-04 2003-04-17 Henkel Kgaa Puder- und Färbehilfsstoffe
DE10230416A1 (de) * 2002-07-06 2004-02-12 Henkel Kgaa Waschmittel mit Textilpflegekomponente auf Cellulosebasis

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2217340A (en) * 1988-04-14 1989-10-25 Unilever Plc Preparation of a granular detergent composition
WO1990015856A1 (fr) * 1989-06-21 1990-12-27 Novo Nordisk A/S Granule d'addition au detergent et detergent
EP0578872A1 (fr) * 1992-07-15 1994-01-19 The Procter & Gamble Company Compositions de détergents
EP0657527A1 (fr) * 1993-12-10 1995-06-14 The Procter & Gamble Company Stabilisation de substances sensibles à l'oxidation dans de compositions détergentes contenant un percarbonate
DE19622443A1 (de) * 1996-06-05 1997-12-11 Henkel Kgaa Granulare Waschmittel, enthaltend optischen Aufheller
DE19801186A1 (de) * 1998-01-15 1999-07-22 Henkel Kgaa Verfahren zur Herstellung gefärbter Wasch- und Reinigungsmittel

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2217340A (en) * 1988-04-14 1989-10-25 Unilever Plc Preparation of a granular detergent composition
WO1990015856A1 (fr) * 1989-06-21 1990-12-27 Novo Nordisk A/S Granule d'addition au detergent et detergent
EP0578872A1 (fr) * 1992-07-15 1994-01-19 The Procter & Gamble Company Compositions de détergents
EP0657527A1 (fr) * 1993-12-10 1995-06-14 The Procter & Gamble Company Stabilisation de substances sensibles à l'oxidation dans de compositions détergentes contenant un percarbonate
DE19622443A1 (de) * 1996-06-05 1997-12-11 Henkel Kgaa Granulare Waschmittel, enthaltend optischen Aufheller
DE19801186A1 (de) * 1998-01-15 1999-07-22 Henkel Kgaa Verfahren zur Herstellung gefärbter Wasch- und Reinigungsmittel

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